A self-regulated gradient interphase for dendrite-free solid-state Li batteries

Wang, Tengrui; Duan, Jian; Bao, Zhenmin; Luo, Wei; Ji, Xiao; Xu, Henghui; Huang, Ying; Huang, Liqiang; Song, Zhenyou; Wen, Jiayun; Chun-sheng, Wang; Huang, Yunhui; Goodenough, John B.

doi:10.1039/d1ee03604a

Cited by 118 publications

(102 citation statements)

References 48 publications

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“…However, the stoichiometry of Li 7 La 3 Zr 2 O 12 is a tetragonal phase with several orders of magnitude lower Li + ionic conductivity than that of cubic phase LLZO. Element doping is used to stabilize the cubic phase structure, such as Al 3+ and Ga 3+ at the lithium site, − Ba 2+ at the lanthanum site, Ta 5+ and Nb 5+ at the zirconium site, − and the F – at the oxygen site. Both the high conductivity and the thorough stability against Li metal are delivered by Ta 5+ doped LLZO.…”

Section: Introductionmentioning

confidence: 99%

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Zhou

Yang

et al. 2022

ACS Appl. Energy Mater.

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Solid-state electrolytes are key materials for developing high-safety solid-state Li-ion batteries. The garnettype Li 7 La 3 Zr 2 O 12 (LLZO) solid electrolyte is one of the most promising solid electrolytes due to its high conductivity and feasible preparation in ambient air. Among several dopants, Tadoped LLZO (Ta-LLZO) delivers high stability against lithium metal and high conductivity, which attracts lots of researchers. However, production of Ta-LLZO ceramics is less problematic due to the complicated gas−liquid−solid sintering mechanism. This work aims to develop an efficient method to produce Ta-LLZO solid electrolyte ceramic pellets, including providing a stacking sintering method and optimizing the amount of excessive Li source, the wet milling duration, and the sintering temperature. First, a low-cost, efficient "gravel-separator" strategy is provided for multiple sintering of LLZO. Second, the Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (Ta5) samples with different excessive Li levels (2, 4, 6, and 8%) are sintered at various sintering conditions of 1240 °C for 60 min, 1280 °C for 20 min, and 1320 °C for 2 min to search for the optimum excessive amount of Li. Third, Ta5 samples with optimized excessive Li (4, 6%) after milling for longer duration are sintered at 1280 °C for 30 min, 1300 °C for 10 min, 1320 °C for 10 min, 1320 °C for 30 min to finally optimize the preparation craft. After optimization, the Ta5 ceramics with excessive 4 and 6% Li sintered at 1320 °C for 10 min deliver homogeneous and dense crosssectional morphology, high conductivity of over 1 × 10 −3 S cm −1 at room temperature, and relative densities of above 96%. Furthermore, symmetric Li cells assembled with the Ta-LLZO solid electrolyte prepared with the optimized method deliver a critical current density of 1.28 mA cm −2 at 30 °C and over 1000 h of stable cycling at 0.2 mA cm −2 (0.2 mA h cm −2 ) at 30 °C.

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Section: Introductionmentioning

confidence: 99%

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Zhou

Yang

et al. 2022

ACS Appl. Energy Mater.

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“…Solid-state lithium batteries (SSLBs) with safe and efficient energy storage have attracted substantial attention to address the undesirable short-circuit issue, severe safety hazard, and performance decay in Li metal batteries. − Effective regulation of solid-state electrolytes (SSEs) for suppressing lithium dendrite growth raises pressing concerns to achieve the practical application of SSLBs. − Garnet-type Ta-doped SSE, Li 6.5 La 3 Zr 1.5 Ta 0.5 O 12 (LLTZO), is an attractive candidate for SSLBs due to its excellent stability against the lithium metal, wide electrochemical window, and high Li-ion conductivity (∼10 –3 S·cm –1 ). − …”

Section: Introductionmentioning

confidence: 99%

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Qin

Xie

Meng

et al. 2022

ACS Appl. Mater. Interfaces

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Solid-state lithium batteries (SSLBs) based on Ta-doped Li6.5La3Zr1.5Ta0.5O12 (LLZTO) suffer from lithium dendrite growth, which hinders their practical application. Herein, first principles simulations indicate that the Ta element prefers to segregate along grain boundaries in the form of Ta2O5 precipitates due to a high energy difference induced by Ta doping. Grain boundary engineering is employed to regulate the distribution of the Ta element and enhance the density of LLZTO by introducing the La2O3 additive. The sufficient La2O3 additive reacts with the Ta2O5 precipitates, while the residual La2O3 nanoparticles fill up void defects, promoting the homogeneous distribution of the Ta element and improving the relative density to ∼98%. Critical current density of the symmetric Li battery reaches 2.12 mA·cm–2 at room temperature with the solid-state electrolyte (LLZTO + 5 wt % La2O3), which increases by 41% compared to pure LLZTO. SSLBs with the LiFePO4 cathode achieve a stable cycling performance with a discharge capacity of 138.6 mA·h·g–1 after 400 cycles at 0.2 C. This work provides theoretical insights into the distribution of Ta-doped LLZTO and inhibits lithium dendrite growth through grain boundary engineering.

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“…To address the interfacial issues, compounding various electrolytes has also been proposed to combine their respective advantages. ( Zhao et al, 2016 ; Wang et al, 2022 ). Therefore, the interfacial compatibility between electrolytes also needs to be studied further.…”

Section: Resultsmentioning

confidence: 99%

Temperature-dependent compatibility study on halide solid-state electrolytes in solid-state batteries

Jia

Deng

et al. 2022

Front. Chem.

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All-solid-state lithium batteries (ASSLBs) have attracted much attention owing to their high safety and energy density compared to conventional organic electrolytes. However, the interfaces between solid-state electrolytes and electrodes retain some knotty problems regarding compatibility. Among the various SSEs investigated in recent years, halide SSEs exhibit relatively good interfacial compatibility. The temperature-dependent interfacial compatibility of halide SSEs in solid-state batteries is investigated by thermal analysis using simultaneous thermogravimetry and differential scanning calorimetry (TG–DSC) and X-ray diffraction (XRD). Halide SSEs, including rock-salt-type Li3InCl6 and anti-perovskite-type Li2OHCl, show good thermal stability with oxides LiCoO2, LiMn2O4, and Li4Ti5O12 up to 320 °C. Moreover, anti-perovskite-type Li2OHCl shows a chemical reactivity with other battery materials (eg., LiFePO4, LiNi0.8Co0.1Mn0.1O2, Si-C, and Li1.3Al0.3Ti1.7(PO4)3) at 320°C, which reaches the melting point of Li2OHCl. It indicated that Li2OHCl has relatively high chemical reactivity after melting. In contrast, rock-salt-type Li3InCl6 shows higher stability and interfacial compatibility. This work delivers insights into the selection of suitable battery materials with good compatibility for ASSLBs.

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A self-regulated gradient interphase for dendrite-free solid-state Li batteries

Abstract: Solid-state Li metal batteries (SSLMBs) have emerged as an important energy storage technology that offers the possibility of both high energy density and safety by combining a Li metal anode...

Cited by 118 publications

References 48 publications

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Temperature-dependent compatibility study on halide solid-state electrolytes in solid-state batteries

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A self-regulated gradient interphase for dendrite-free solid-state Li batteries

Abstract: Solid-state Li metal batteries (SSLMBs) have emerged as an important energy storage technology that offers the possibility of both high energy density and safety by combining a Li metal anode...

Cited by 118 publications

References 48 publications

Production of Ta-Doped Li7La3Zr2O12 Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li7La3Zr2O12 Solid Electrolyte with High Critical Current Density

Grain Boundary Engineering in Ta-Doped Garnet-Type Electrolyte for Lithium Dendrite Suppression

Temperature-dependent compatibility study on halide solid-state electrolytes in solid-state batteries

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Product

Resources

About

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density

Production of Ta-Doped Li₇La₃Zr₂O₁₂ Solid Electrolyte with High Critical Current Density